CN114933289A - Co-production process for glyphosate and ferric phosphate - Google Patents
Co-production process for glyphosate and ferric phosphate Download PDFInfo
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- CN114933289A CN114933289A CN202210711446.XA CN202210711446A CN114933289A CN 114933289 A CN114933289 A CN 114933289A CN 202210711446 A CN202210711446 A CN 202210711446A CN 114933289 A CN114933289 A CN 114933289A
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- Prior art keywords
- glyphosate
- solution
- iron
- phosphoric acid
- phosphate
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 177
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 177
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 60
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 30
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 30
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 156
- 239000012528 membrane Substances 0.000 claims abstract description 99
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 92
- 230000003647 oxidation Effects 0.000 claims abstract description 89
- 239000012452 mother liquor Substances 0.000 claims abstract description 87
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 78
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 75
- 239000011574 phosphorus Substances 0.000 claims abstract description 75
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 67
- 238000000926 separation method Methods 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 230000032683 aging Effects 0.000 claims abstract description 41
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000000909 electrodialysis Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 238000006479 redox reaction Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 115
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 66
- 239000002253 acid Substances 0.000 claims description 40
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000012043 crude product Substances 0.000 claims description 26
- 230000001590 oxidative effect Effects 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 230000009471 action Effects 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 23
- 230000008025 crystallization Effects 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000002699 waste material Substances 0.000 abstract description 12
- 238000004090 dissolution Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 238000003860 storage Methods 0.000 description 22
- 238000011084 recovery Methods 0.000 description 19
- 235000011121 sodium hydroxide Nutrition 0.000 description 19
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 16
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- -1 orthophosphate ions Chemical class 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 12
- 239000010452 phosphate Substances 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- YWICANUUQPYHOW-UHFFFAOYSA-M sodium;2-(phosphonomethylamino)acetate Chemical compound [Na+].OP(O)(=O)CNCC([O-])=O YWICANUUQPYHOW-UHFFFAOYSA-M 0.000 description 4
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 3
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- XAKRTGZVYPZHCO-UHFFFAOYSA-O hydroxy-methoxy-oxophosphanium Chemical compound CO[P+](O)=O XAKRTGZVYPZHCO-UHFFFAOYSA-O 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- FKSLYSSVKFYJKE-UHFFFAOYSA-N n,n-diethylethanamine;methanol Chemical compound OC.CCN(CC)CC FKSLYSSVKFYJKE-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 230000026683 transduction Effects 0.000 description 1
- 238000010361 transduction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a co-production process for glyphosate and ferric phosphate, and belongs to the technical field of waste liquid recycling in glyphosate production. Taking glyphosate mother liquor formed in glyphosate production as a raw material, and performing membrane separation, high-temperature oxidation, bipolar membrane electrodialysis, iron dissolving reaction, redox reaction and aftertreatment to obtain an iron phosphate product; wherein the post-treatment comprises aging, filtering, washing and drying; preferably, the phosphoric acid involved in the aging process is obtained by taking glyphosate mother liquor formed in glyphosate production as a raw material and performing membrane separation, high-temperature oxidation, crystallization, filtration, dissolution, bipolar membrane electrodialysis and dilution. The utilization rate and economic benefit of phosphorus resources are improved, 100% self-sufficiency of the phosphorus resources in the iron phosphate production process is guaranteed, three wastes are not increased, and the prepared iron phosphate has few impurities, is easy to purify and has stable product quality.
Description
Technical Field
The invention relates to a co-production process for glyphosate and ferric phosphate, and belongs to the technical field of waste liquid recycling in glyphosate production.
Background
Glyphosate is one of the most prevalent herbicides, having systemic transduction, broad spectrum biocidal properties. The production process generally adopts an alkyl esterification process (developed by Shenyang chemical research institute) taking glycine, paraformaldehyde and dimethyl phosphite as raw materials, wherein a large amount of phosphorus-containing mother liquor is generated during the synthesis of glyphosate, and a large amount of sodium chloride exists in the phosphorus-containing mother liquor. At present, the glyphosate mother liquor has more treatment methods, but the byproduct phosphate is mainly used. Taking a high-temperature wet catalytic oxidation process as an example, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate can be by-produced by controlling the pH value of the system; of these, disodium hydrogen phosphate by-product is taken as an example, and 1 ton of glyphosate is produced on average, and more than 1 ton of disodium hydrogen phosphate dodecahydrate solid can be obtained. And in the treatment process of the glyphosate mother liquor, a membrane separation technology and/or a bipolar membrane electrodialysis technology are/is involved, and the treatment process specifically comprises the following steps:
the membrane separation technology refers to a separation technology which realizes selectivity when a mixture of molecules with different particle diameters passes through a semipermeable membrane. The membrane is divided into a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane and the like according to the aperture of the filtration membrane, and has the functions of separation, concentration, purification and refinement;
when the bipolar membrane electrodialysis process is used for treating high-salt wastewater, the salt solution can be directly prepared into corresponding acid and alkali under the action of an electric field and a selective permeation membrane. Under increasingly strict environmental protection requirements, the application field of the method is increasingly wide, and the process is mature;
however, according to the existing treatment processes, economic benefits can not be realized, and the effective recovery and utilization of phosphorus resources in the glyphosate mother liquor can not be realized.
In the prior art, CN102786187A solves the problems of high cost and resource recycling in glyphosate mother liquor treatment, and provides an integrated process for comprehensively recycling glyphosate mother liquor.
CN103864040A discloses a process for preparing disodium hydrogen phosphate from glyphosate mother liquor, which comprises the following steps: an oxidation step, oxidizing the organic phosphorus compound and phosphorous acid in the glyphosate mother liquor into orthophosphate ions by taking oxygen in the air as an oxidant under the reaction conditions of 240-320 ℃ and 6.0-15.0Mpa pressure range; the oxygen supply amount is 0.7-1.3 times of the total amount of the COD of the glyphosate mother liquor; a crystallization step, cooling the oxidation liquid in the step 1 to-5-12 ℃, and generating solid disodium hydrogen phosphate dodecahydrate crystals under the conditions of pH7.0-pH10.5; and a separation step of solid-liquid separating the oxidized liquid crystallized in the step 2.
CN105236373A discloses a process for producing phosphate from phosphorous acid raffinate, which comprises the steps of adding sodium hydroxide or potassium hydroxide to phosphorous acid raffinate in the phosphorous acid production process, carrying out catalytic oxidation under the ultraviolet illumination condition, then adding sodium hydroxide or potassium hydroxide, and carrying out post-treatment to obtain a corresponding phosphate product. The invention solves the problem of recycling residual liquid after the mother solution of the phosphorous acid is repeatedly used in the phosphorous acid production, converts the dangerous waste of the residual liquid of the phosphorous acid into a phosphate product, reduces the treatment cost and well recycles the phosphorus resource.
And CN108117055A discloses a "preparation method and a production apparatus for battery-grade iron phosphate", wherein the production apparatus includes an iron salt storage tank, a phosphate storage tank, a reaction kettle, a retention kettle and a plate frame, the iron salt storage tank and the phosphate storage tank are respectively communicated to the top of the reaction kettle through a material conveying pipeline, the reaction kettle, the retention kettle and the plate frame are sequentially connected, and a production apparatus adopting continuous feeding and discharging is adopted to make an oxidation precipitation reaction in a dynamic balance state, so that the reaction time is short, the quality of the produced iron phosphate is stable, the particle size is controllable, and the continuous industrial production of the iron phosphate is realized.
Disclosure of Invention
The invention combines the characteristics of the existing glyphosate production process, namely, the phosphoric acid glyphosate mother liquor is generated, and the generated phosphoric acid glyphosate mother liquor is used for preparing the iron phosphate after being respectively treated by a series of treatments, so as to improve the utilization rate and the economic benefit of the phosphoric resource, ensure 100 percent self-sufficiency of the phosphoric resource in the iron phosphate production process, avoid increasing three wastes, and the prepared iron phosphate has less impurities, easy purification and stable product quality, thereby providing the co-production process for the glyphosate and the iron phosphate.
In order to achieve the technical purpose, the following technical scheme is proposed:
the technical scheme provides: a co-production process for glyphosate and ferric phosphate specifically comprises the following steps:
1) membrane separation: and (3) carrying out membrane separation on the glyphosate mother liquor under the condition that the pH value is 7-10 to obtain an organic phosphorus solution and a sodium chloride solution. So as to reduce the corrosion of the glyphosate mother liquor to the metal material to the maximum extent, wherein in the organophosphorus solution, the mol ratio of chloride ions to phosphorus atoms is controlled to be 0-1: 1;
2) high-temperature oxidation: adding an oxidant (oxygen or hydrogen peroxide) into the obtained organic phosphorus solution at the temperature of 200-374 ℃ under the conditions of 3-8 Mpa and taking inorganic salts of one or more transition elements in the fourth period of the periodic table of elements as catalysts, and carrying out oxidation reaction to obtain a mixed oxidation solution containing disodium hydrogen phosphate, wherein the disodium hydrogen phosphate is mainly contained in the mixed oxidation solution;
3) electrodialysis: and 3) carrying out electrodialysis on part of the mixed oxidation liquid obtained in the step 2) under the action of a direct-current electric field and a bipolar membrane formed by compounding an anion exchange membrane and a cation exchange membrane to obtain liquid alkali and mixed acid, wherein the mixed acid comprises phosphoric acid and hydrochloric acid, and the molar ratio of the hydrochloric acid to the phosphoric acid in the mixed acid is controlled to be 0-1: 1; the obtained liquid caustic soda can be directly sold after being concentrated;
4) and (3) iron dissolution reaction: reacting the obtained mixed acid with iron powder at the temperature of 30-80 ℃ to obtain hydrogen and ferrous reaction liquid; wherein the dosage ratio of the phosphoric acid to the iron powder in the mixed acid is 1.5-3: 1;
5) oxidation-reduction reaction: adding hydrogen peroxide into the obtained ferrous reaction liquid, and carrying out redox reaction at the temperature of 30-80 ℃ to obtain iron phosphate slurry, wherein the molar ratio of the iron powder to the hydrogen peroxide is 1: 0.5-1; filtering to obtain a crude iron phosphate product and an iron phosphate reaction mother solution; controlling the molar ratio of phosphorus atoms to iron atoms in the crude iron phosphate product to be 1-2: 1;
6) and (3) post-treatment: adding the obtained iron phosphate crude product into an aging kettle by taking the adding amount of a phosphoric acid solution with the concentration of 0.5-5% as 10-20 times of the mass of the iron phosphate crude product, adding a phosphoric acid solution with the concentration of 0.5-5%, aging at the temperature of 80-100 ℃, filtering, washing and drying to obtain an iron phosphate product and an aging mother liquor containing phosphoric acid, wherein the iron phosphate product is stored and directly sold; the aging mother liquor containing phosphoric acid can be directly reused for iron dissolving reaction in the step 4);
wherein the preparation process of the phosphoric acid solution with the concentration of 0.5-5% comprises the following steps:
cooling and crystallizing the other part of the mixed oxidation liquid obtained in the step 2) at the temperature of-15-20 ℃, and filtering to obtain a disodium hydrogen phosphate solid; adding water to dissolve the obtained disodium hydrogen phosphate solid, and controlling to obtain a disodium hydrogen phosphate solution with the concentration of 5-10%; obtaining liquid caustic soda and a phosphoric acid solution with the concentration of 9-10% under the action of an electric field of a bipolar membrane electrodialysis system, wherein the liquid caustic soda can be directly sold for the outside after being concentrated, and the obtained phosphoric acid solution with the concentration of 9-10% is diluted to obtain a phosphoric acid solution with the concentration of 0.5-5%, and then the phosphoric acid solution is used for an aging reaction of a crude iron phosphate product;
during the aging reaction process of the iron phosphate crude product, removing other anions in the iron phosphate crude product so as to improve the purity of the iron phosphate and reduce impurities contained in the iron phosphate;
the volume ratio of the partial mixed oxidation liquid to the other partial mixed oxidation liquid is 10-20: in the limitation, most of mixed oxidation liquid is used for preparing mixed acid (including hydrochloric acid and phosphoric acid), and then the mixed acid is reacted with iron powder, so that the reaction rate can be greatly improved, and excessive use of phosphoric acid is avoided, wherein although the related mixed acid contains certain impurities, the requirement of iron dissolution reaction can be met, and 90% of load in a disodium hydrogen phosphate crystallization process is reduced, namely energy consumption is reduced; crystallizing a small part of mixed oxidation liquid to obtain a disodium hydrogen phosphate solid, and preparing phosphoric acid, wherein the related phosphoric acid is pure phosphoric acid and is used for aging reaction of a crude iron phosphate product, so that the purity of the iron phosphate product can be effectively increased.
Preferably, in step 5), the ferric phosphate reaction mother liquor is concentrated and then subjected to membrane separation together with the glyphosate mother liquor, so that the ferric phosphate reaction mother liquor is recycled and reused without a new wastewater treatment system.
Preferably, in step 1), the glyphosate mother liquor refers to: and recovering acid glyphosate mother liquor discharged from a glyphosate production process by using a catalyst triethylamine to obtain alkaline glyphosate mother liquor with the pH value of 9-10, wherein the alkaline glyphosate mother liquor comprises sodium phosphite, glyphosate sodium salt, glyphosine sodium salt, sodium chloride, sodium hydroxide and the like.
Wherein, the production process of the glyphosate comprises the following steps:
x1: adding yellow phosphorus and chlorine into a chlorination reaction device with a phosphorus washing tower, and carrying out chlorination reaction at the temperature of 80-90 ℃ to generate phosphorus trichloride;
x2: introducing methanol and the obtained phosphorus trichloride into an esterification reaction device, carrying out esterification reaction under the condition of-80 KPa to-90 KPa, and then generating a dimethyl phosphite crude product through a deacidification kettle, wherein the dimethyl phosphite crude product comprises dimethyl phosphite, monomethyl phosphite, phosphorous acid and methanol;
x3: introducing the obtained dimethyl phosphite crude product into a rectifying device, and carrying out rectification separation reaction under the condition of-90 kpa to respectively obtain rectification residual liquid and dimethyl phosphite;
x4: introducing the obtained dimethyl phosphite into a synthesis reaction device, and synthesizing glyphosate precursor with glycine and paraformaldehyde in a methanol-triethylamine system;
x5: introducing the obtained glyphosate precursor into an acidolysis device, and carrying out acidolysis under the hydrochloric acid condition to obtain glyphosate acidolysis solution;
x6: introducing the obtained glyphosate acidolysis solution into a glyphosate crystallization device, adding liquid caustic soda to adjust the pH value, and crystallizing; separating by a glyphosate separation device to respectively obtain acidic glyphosate mother liquor and glyphosate crude product, washing and drying the obtained glyphosate crude product to obtain glyphosate solid, and storing the glyphosate solid in a glyphosate finished product tank; the acidic glyphosate mother liquor is treated by a catalyst triethylamine recovery device to obtain alkaline glyphosate mother liquor, namely the raw material for preparing the ferric phosphate by the technical scheme.
Wherein, the obtained rectification residual liquid is hydrolyzed, concentrated and crystallized to obtain phosphorous acid with the purity of 99 percent, and the phosphorous acid is directly sold. The utilization rate of the waste liquid discharged in the glyphosate production process is improved, namely, the utilization of phosphorus resources is realized, the discharge of the waste liquid is reduced, and the recycling of the waste liquid is realized.
By adopting the technical scheme, the beneficial technical effects brought are as follows:
the method combines the characteristics of the existing glyphosate production process, namely, after the generated glyphosate mother liquor is subjected to membrane separation and high-temperature oxidation, mixed oxidation liquid mainly comprising disodium hydrogen phosphate and sodium chloride is obtained, part of the mixed oxidation liquid is subjected to electrodialysis to obtain mixed acid of phosphoric acid and hydrochloric acid, and then the mixed acid reacts with iron powder to prepare the iron phosphate, so that the reaction rate can be greatly improved, and more than 90% of mixed liquid is prevented from extracting the disodium hydrogen phosphate in a cooling crystallization mode, so that the load of a disodium hydrogen phosphate crystallization process is effectively reduced, and the energy consumption is reduced; the synthesized ferric phosphate reaction mother liquor can be returned to the glyphosate mother liquor without newly establishing a wastewater treatment system;
cooling, crystallizing, filtering and dissolving the other part of the obtained mixed oxidation liquid to obtain a disodium hydrogen phosphate solution, performing electrodialysis to obtain pure phosphoric acid, aging the pure phosphoric acid and the obtained iron phosphate crude product (containing certain impurities), namely removing anionic impurities in the iron phosphate crude product, further improving the purity of the iron phosphate, and further realizing 100% recovery of phosphorus resources in the glyphosate mother liquid and self-sufficiency of the phosphorus resources;
in the invention, after the glyphosate mother liquor discharged in the glyphosate production process is recovered by a catalyst triethylamine, the obtained alkaline glyphosate mother liquor is used as a raw material to prepare corresponding phosphoric acid and/or hydrochloric acid, and then the phosphoric acid and/or hydrochloric acid is used for preparing iron phosphate, so that the feasibility of the co-production process of the glyphosate and the iron phosphate is better realized, and three wastes are not increased.
Drawings
Fig. 1 is a block diagram showing a co-production system of glyphosate and iron phosphate according to example 1;
FIG. 2 is a block diagram showing the construction of a phosphoric acid production system according to example 2;
FIG. 3 is a block diagram showing the construction of a system for producing glyphosate according to example 3;
fig. 4 is a block diagram showing a co-production system of glyphosate and iron phosphate according to example 4.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The method comprises the steps of taking glyphosate mother liquor generated in a glyphosate production process as a raw material, carrying out triethylamine recovery as a catalyst, membrane separation, high-temperature oxidation, bipolar membrane electrodialysis, iron dissolving reaction, redox reaction and aging reaction, and carrying out filtering, washing and drying to obtain an iron phosphate product. The specific process is as follows:
1. adding liquid alkali into glyphosate mother liquor (acidity) generated in the glyphosate production process, adjusting the pH value to 9-10, dissociating triethylamine serving as a catalyst, separating oil-water, rectifying and recovering the triethylamine serving as the catalyst to obtain alkaline glyphosate mother liquor. Wherein the alkaline glyphosate mother liquor mainly comprises sodium phosphite, glyphosate sodium salt, glyphosine sodium salt, sodium chloride and excessive sodium hydroxide;
2. under the condition that the pH value is 7-10, removing mechanical impurities from the alkaline glyphosate mother liquor by a membrane separation device, and filtering out most of sodium chloride to obtain an organic phosphorus solution;
3. introducing an organic phosphorus solution into an organic phosphorus solution oxidation device, and introducing an oxidant (oxygen or hydrogen peroxide) for oxidation under the conditions of 3-8 Mpa, 200-374 ℃ and a catalyst, wherein macromolecular phosphorus-containing organic matters are oxidized into carbon dioxide and phosphoric acid to obtain an inorganic phosphorus solution containing a small amount of sodium chloride, namely a mixed oxidation solution mainly containing disodium hydrogen phosphate;
4. introducing the mixed oxidation solution into a bipolar membrane device, and obtaining a sodium hydroxide solution with the concentration of about 8% and a mixed acid solution (namely a mixture of phosphoric acid and hydrochloric acid) under the action of an exchange membrane formed by compounding an electric field and anions and cations;
5. reacting mixed acid and iron powder in an iron dissolving device at the temperature of 30-80 ℃, wherein the adding amount ratio of the mixed acid to the iron powder is that the molar weight ratio of phosphorus element to iron in the mixed acid is 1.5-3: 1, counting; simultaneously, releasing hydrogen to obtain ferrous reaction liquid containing ferrous dihydrogen phosphate, ferrous hydrogen phosphate and the like;
6. adding hydrogen peroxide into the ferrous reaction liquid, wherein the using amount of the hydrogen peroxide is 0.5-1 time of the molar amount of the iron powder, carrying out redox reaction at 30-80 ℃, completely oxidizing ferrous into ferric iron, and filtering to obtain a ferric phosphate crude product and a ferric phosphate reaction mother liquid;
7. putting the iron phosphate crude product into an aging kettle filled with a phosphoric acid solution with the concentration of 0.5-5%, and aging for 4-20 h at the temperature of 80-100 ℃;
8. filtering the aging solution, thoroughly cleaning, and drying at 100 ℃ to obtain a ferric phosphate dihydrate product; and sintering the ferric phosphate dihydrate at the high temperature of 500 ℃ to obtain the anhydrous ferric phosphate product.
Wherein, the related phosphoric acid solution with the concentration of 0.5-5% is prepared after directly purchasing phosphoric acid.
The related glyphosate production process adopts the existing mature technology to prepare glyphosate.
In addition, the related co-production system of glyphosate and ferric phosphate is as follows:
as shown in fig. 1: the glyphosate production system adopts a glyphosate production system in the prior art, wherein the glyphosate production system comprises a glyphosate separation device;
the iron phosphate production system includes: the glyphosate mother liquor temporary storage tank is connected with the glyphosate separation device, and is connected with a glyphosate production system;
the organic phosphorus solution oxidation device is arranged at the rear side of a station of the membrane separation device, and an organic phosphorus solution outlet on the membrane separation device is connected with a feed inlet in the organic phosphorus solution oxidation device; the bipolar membrane device is arranged at the rear side of a station of the organic phosphorus solution oxidation device, and an upper discharge port of the organic phosphorus solution oxidation device is connected with an upper feed port of the bipolar membrane device; the iron dissolving device is arranged on the rear side of a station of the bipolar membrane device, and an acid outlet on the bipolar membrane device is connected with an acid inlet on the iron dissolving device; the ferrous oxidation kettle is arranged at the rear side of the station of the iron dissolving device, and a solution outlet on the iron dissolving device is connected with the ferrous oxidation kettle; the aging kettle is arranged at the rear side of the working position of the ferrous oxidation kettle, and the ferrous oxidation kettle is connected with the aging kettle; the filtering device is arranged at the rear side of the station of the aging kettle, and the aging kettle is connected with the filtering device; the washing device is arranged at the rear side of the station of the filtering device, and the filtering device is connected with the washing device; the drying box is arranged on the rear side of a station of the washing device, the washing device is connected with the drying box, and the drying box is connected with a finished iron phosphate tank;
a continuous passage for preparing the iron phosphate by taking the glyphosate mother liquor as a raw material is formed among the glyphosate mother liquor temporary storage tank, the membrane separation device, the organic phosphorus solution oxidation device, the bipolar membrane device, the iron dissolving device, the ferrous oxidation kettle, the aging kettle, the filtering device, the washing device and the drying box.
In addition, a triethylamine recovery tank is arranged between the glyphosate mother liquor temporary storage tank and the membrane separation device, and the triethylamine recovery tank is connected with a liquid caustic soda inlet pipe;
a membrane separation device: comprises a selective permeable membrane and a semi-permeable membrane;
organic phosphorus solution oxidation unit: an oxidant inlet pipe is connected, wherein the organic phosphorus solution is converted into an inorganic phosphorus solution under the action of an oxidant;
a bipolar membrane device: comprises an exchange membrane formed by compounding anions and cations;
and (3) iron melting device: is connected with an iron powder feeding pipe, wherein, the iron powder reacts with mixed acid formed by bipolar membrane treatment to generate ferrous solution;
a ferrous iron oxidation kettle: a hydrogen peroxide inlet pipe is connected, and in a ferrous oxidation kettle, ferrous ions in a ferrous solution and hydrogen peroxide are subjected to oxidation-reduction reaction to generate iron ions, so that preparation conditions are provided for the subsequent generation of iron phosphate;
in the organic phosphorus solution oxidation device, the related principle comprises the following components: oxidizing organic phosphorus into inorganic phosphorus under the action of an oxidizing agent, and enabling the inorganic phosphorus to exist in a solution in a phosphate radical form, wherein the method also comprises the step of oxidizing phosphite radicals into phosphate radicals;
in a bipolar membrane device, the reaction formula involved includes:
in the iron dissolving device, the involved reaction formula comprises:
in a ferrous oxidation kettle, the involved reaction formula comprises:
in an iron phosphate aging kettle, the involved reaction formula comprises:
example 2
The method comprises the steps of taking glyphosate mother liquor generated in a glyphosate production process as a raw material, and obtaining phosphoric acid through triethylamine recovery as a catalyst, membrane separation, high-temperature oxidation, cooling crystallization and bipolar membrane electrodialysis. The specific process is as follows:
1. adding liquid alkali into glyphosate mother liquor (acidity) generated in the glyphosate production process, adjusting the pH value to 9-10, dissociating catalyst triethylamine, and recovering the catalyst triethylamine through an oil-water separation device and a rectification device to obtain alkaline glyphosate mother liquor. Wherein the alkaline glyphosate mother liquor mainly comprises sodium phosphite, glyphosate sodium salt, glyphosine sodium salt, sodium chloride and excessive sodium hydroxide;
2. under the condition that the pH value is 7-10, removing mechanical impurities from the alkaline glyphosate mother liquor by a membrane separation device, and filtering out most of sodium chloride to obtain an organic phosphorus solution;
3. introducing the organic phosphorus solution into a high-temperature oxidation device, and introducing an oxidant (oxygen or hydrogen peroxide) for oxidation under the conditions of 3-8 Mpa, 200-374 ℃ and a catalyst, wherein macromolecular phosphorus-containing organic matters are oxidized into carbon dioxide and phosphoric acid to obtain an inorganic phosphorus solution containing a small amount of sodium chloride, namely a mixed oxidation solution mainly containing disodium hydrogen phosphate;
4. cooling the mixed oxidation liquid to-15-20 ℃, crystallizing, and leaching to obtain pure disodium hydrogen phosphate dodecahydrate solid; putting pure disodium hydrogen phosphate dodecahydrate solid into deionized water to prepare a 5-10% disodium hydrogen phosphate solution;
5. and (3) introducing a 5-10% disodium hydrogen phosphate solution into a bipolar membrane device, and under the action of an electric field and an exchange membrane formed by compounding anions and cations, obtaining a sodium hydroxide solution with the concentration of about 8% and a phosphoric acid solution with the concentration of about 10%.
Wherein the obtained phosphoric acid can be sold directly or prepared into a phosphoric acid solution with the concentration of 0.5-5%, and then participates in the aging reaction of the iron phosphate crude product.
In addition, the phosphoric acid preparation system is as follows:
as shown in fig. 2: the device comprises a glyphosate mother liquor temporary storage tank, a membrane separation device, an organic phosphorus solution oxidation device, a crystallization device and a bipolar membrane device which are connected with a glyphosate production system, wherein the glyphosate mother liquor temporary storage tank is arranged on the front side of a station of the membrane separation device and is connected with the glyphosate separation device in the glyphosate production system;
the organic phosphorus solution oxidation device is arranged at the rear side of a station of the membrane separation device, and an organic phosphorus solution outlet on the membrane separation device is connected with a feed inlet in the organic phosphorus solution oxidation device; the crystallization device is arranged at the rear side of a station of the organic phosphorus solution oxidation device, and the organic phosphorus solution oxidation device is connected with an upper feed inlet of the crystallization device; an elution device and a dissolution device are arranged between the crystallization device and the bipolar membrane device, the elution device is arranged on the rear side of a station of the crystallization device, the dissolution device is arranged on the rear side of the station of the elution device, the bipolar membrane device is arranged on the rear side of the station of the dissolution device, the dissolution device is connected with an upper feed inlet of the bipolar membrane device, and an upper acid outlet of the bipolar membrane device is connected with a phosphoric acid product tank;
a continuous passage for preparing phosphoric acid by taking the glyphosate mother liquor as a raw material is formed among the glyphosate mother liquor temporary storage tank, the membrane separation device, the organic phosphorus solution oxidation device, the crystallization device, the leaching device, the dissolving device and the bipolar membrane device.
The glyphosate production system adopts a glyphosate production system in the prior art, and comprises a glyphosate separation device. In addition, a triethylamine recovery tank is arranged between the glyphosate mother liquor temporary storage tank and the membrane separation device, and the triethylamine recovery tank is connected with a liquid caustic soda inlet pipe;
a membrane separation device: comprises a selective permeation membrane and a semi-permeable membrane;
organic phosphorus solution oxidation unit: an oxidant inlet pipe is connected, wherein the organic phosphorus solution is converted into an inorganic phosphorus solution under the action of an oxidant;
a bipolar membrane device: comprises an exchange membrane formed by compounding anions and cations;
in an organophosphorus solution oxidation device, the involved principle comprises: the organic phosphorus is oxidized into inorganic phosphorus under the action of an oxidant and exists in the solution in the form of phosphate radical, wherein the method also comprises the step of oxidizing phosphite radical into phosphate radical;
in a bipolar membrane device, the principles/equations involved include:
example 3
The embodiment provides a production process of glyphosate, which specifically comprises the following steps:
x1: adding yellow phosphorus and chlorine into a chlorination reaction device with a phosphorus washing tower, and carrying out chlorination reaction at the temperature of 80-90 ℃ to generate phosphorus trichloride;
x2: introducing methanol and the obtained phosphorus trichloride into an esterification reaction device, carrying out esterification reaction under the condition of-80 to-90 KPa, and then generating a dimethyl phosphite crude product through a deacidification kettle, wherein the dimethyl phosphite crude product comprises dimethyl phosphite, monomethyl phosphite, phosphorous acid and methanol;
x3: introducing the obtained dimethyl phosphite crude product into a rectifying device, and carrying out rectification separation reaction under the condition of-90 kpa to respectively obtain rectification residual liquid and dimethyl phosphite;
x4: introducing the obtained dimethyl phosphite into a synthesis reaction device, and synthesizing glyphosate precursor with glycine and paraformaldehyde in a methanol-triethylamine system;
x5: introducing the obtained glyphosate precursor into an acidolysis device, and carrying out acidolysis under the hydrochloric acid condition to obtain glyphosate acidolysis solution;
x6: introducing the obtained glyphosate acidolysis solution into a glyphosate crystallization device, adding liquid caustic soda to adjust the pH value, and crystallizing; separating by a glyphosate separation device to respectively obtain acidic glyphosate mother liquor and glyphosate crude product, washing and drying the obtained glyphosate crude product to obtain a glyphosate finished product, and storing the glyphosate finished product in a glyphosate finished product tank; the acidic glyphosate mother liquor is treated by a catalyst triethylamine recovery device to obtain alkaline glyphosate mother liquor, namely the raw material for preparing the ferric phosphate by the technical scheme.
Wherein, the obtained rectification residual liquid is hydrolyzed, concentrated and crystallized to obtain phosphorous acid with the purity of 99 percent, and the phosphorous acid is directly sold for external use. The utilization rate of the waste liquid discharged in the glyphosate production process is improved, namely, the utilization of phosphorus resources is realized, the discharge of the waste liquid is reduced, and the recycling of the waste liquid is realized.
In addition, the production system of the glyphosate is as follows:
as shown in fig. 3: the device comprises a chlorination reaction device for converting yellow phosphorus and chlorine into phosphorus trichloride, an esterification reaction device for converting phosphorus trichloride and methanol into dimethyl phosphite, a rectification device for rectifying dimethyl phosphite, a synthesis reaction device for generating glyphosate from dimethyl phosphite, glycine and paraformaldehyde, an acidolysis device, a glyphosate crystallization device and a glyphosate separation device, wherein the chlorination reaction device is arranged on the front side of a station of the esterification reaction device and is connected with the esterification reaction device; the rectification device is arranged at the rear side of the station of the esterification reaction device, and the esterification reaction device is connected with the rectification device; a synthesis reaction device is arranged at the rear side of the station of the rectifying device, and the rectifying device is connected with the synthesis reaction device; the acidolysis device is arranged at the rear side of the station of the synthesis reaction device, and the synthesis reaction device is connected with the acidolysis device; the glyphosate crystallization device is arranged at the rear side of the station of the acidolysis device, and the acidolysis device is connected with the glyphosate crystallization device; the glyphosate separating device is arranged at the rear side of a station of the glyphosate crystallizing device, the glyphosate crystallizing device is connected with the glyphosate separating device, and the glyphosate separating device is connected with a glyphosate finished product tank;
a continuous path for generating glyphosate is formed among the chlorination reaction device, the esterification reaction device, the rectification device, the synthesis reaction device, the acidolysis device, the glyphosate crystallization device and the glyphosate separation device.
Wherein a glyphosate washing device and a glyphosate drying device are arranged between the glyphosate separating device and the glyphosate finished product tank.
A glyphosate mother liquor temporary storage tank is also arranged at the rear side of the station of the glyphosate separation device, and the glyphosate separation device is connected with the glyphosate mother liquor temporary storage tank; a triethylamine recovery tank is arranged on the rear side of a station of the glyphosate mother liquor temporary storage tank, the glyphosate mother liquor temporary storage tank is connected with the triethylamine recovery tank, and a liquid caustic soda inlet pipe is connected to the triethylamine recovery tank to realize the recovery of catalyst triethylamine, so that the phosphorus-containing alkaline glyphosate mother liquor is finally formed and can be further treated and recovered.
A rectification raffinate hydrolysis device is also arranged at the rear side of the station of the rectification device, and the rectification device is connected with the rectification raffinate hydrolysis device; a concentration device is arranged at the rear side of the station of the rectification raffinate hydrolysis device, and the rectification raffinate hydrolysis device is connected with the concentration device; the station rear side of enrichment facility is equipped with the phosphorous acid crystallization device, and enrichment facility is connected with the phosphorous acid crystallization device, realizes the recovery of phosphorous acid.
In the chlorination reaction device, the related reaction formula is as follows:
in the esterification reaction device, the involved reaction formula is as follows:
in a glyphosate synthesis reaction device, the reaction formula is as follows:
in the acidolysis device, the involved reaction formula is as follows:
in a rectification raffinate hydrolysis device, the involved reaction formula is as follows:
example 4
The embodiment provides a co-production process for glyphosate and ferric phosphate, which specifically comprises the following steps:
1) membrane separation: and (3) carrying out membrane separation on the glyphosate mother liquor under the condition that the pH value is 7-10 to obtain an organic phosphorus solution and a sodium chloride solution. So as to reduce the corrosion of the glyphosate mother liquor to the metal material to the maximum extent, wherein in the organophosphorus solution, the mol ratio of chloride ions to phosphorus atoms is controlled to be 0-1: 1;
2) high-temperature oxidation: adding an oxidant (oxygen or hydrogen peroxide) into the obtained organic phosphorus solution at the temperature of 200-374 ℃ under the conditions of 3-8 Mpa and taking inorganic salts of one or more transition elements in the fourth period of the periodic table of elements as catalysts, and carrying out oxidation reaction to obtain a mixed oxidation solution containing disodium hydrogen phosphate, wherein the disodium hydrogen phosphate is mainly contained in the mixed oxidation solution;
3) electrodialysis: and 3) carrying out electrodialysis on part of the mixed oxidation liquid obtained in the step 2) under the action of a direct-current electric field and a bipolar membrane formed by compounding an anion exchange membrane and a cation exchange membrane to obtain liquid alkali and mixed acid, wherein the mixed acid comprises phosphoric acid and hydrochloric acid, and the molar ratio of the hydrochloric acid to the phosphoric acid in the mixed acid is controlled to be 0-1: 1; the obtained liquid alkali can be directly sold for external use after being concentrated;
4) and (3) iron dissolution reaction: reacting the obtained mixed acid with iron powder at 30-80 ℃ to obtain hydrogen and ferrous reaction liquid; wherein, the dosage ratio of the phosphoric acid to the iron powder in the mixed acid is 1.5-3: 1;
5) oxidation-reduction reaction: adding hydrogen peroxide into the obtained ferrous reaction liquid, and carrying out redox reaction at the temperature of 30-80 ℃ to obtain iron phosphate slurry, wherein the molar ratio of the iron powder to the hydrogen peroxide is 1: 0.5-1; filtering to obtain a ferric phosphate crude product and a ferric phosphate reaction mother solution; controlling the molar ratio of phosphorus atoms to iron atoms in the crude iron phosphate product to be 1-2: 1;
6) and (3) post-treatment: adding the obtained iron phosphate crude product into an aging kettle by taking the adding amount of a phosphoric acid solution with the concentration of 0.5-5% as 10-20 times of the mass of the iron phosphate crude product, adding a phosphoric acid solution with the concentration of 0.5-5%, aging at the temperature of 80-100 ℃, filtering, washing and drying to obtain an iron phosphate product and an aging mother liquor containing phosphoric acid, wherein the iron phosphate product is stored and directly sold; the aging mother liquor containing phosphoric acid can be directly reused for iron dissolving reaction in the step 4);
wherein the preparation process of the phosphoric acid solution with the concentration of 0.5-5% comprises the following steps:
cooling and crystallizing the other part of the mixed oxidation liquid obtained in the step 2) at the temperature of-15-20 ℃, and filtering to obtain a disodium hydrogen phosphate solid; adding water to dissolve the obtained disodium hydrogen phosphate solid, and controlling to obtain a disodium hydrogen phosphate solution with the concentration of 5-10%; obtaining liquid caustic soda and a phosphoric acid solution with the concentration of 9-10% under the action of an electric field of a bipolar membrane electrodialysis system, wherein the liquid caustic soda can be directly sold for the outside after being concentrated, and the obtained phosphoric acid solution with the concentration of 9-10% is diluted to obtain a phosphoric acid solution with the concentration of 0.5-5%, and then the phosphoric acid solution is used for an aging reaction of a crude iron phosphate product;
during the aging reaction process of the iron phosphate crude product, removing other anions in the iron phosphate crude product so as to improve the purity of the iron phosphate and reduce impurities contained in the iron phosphate;
the volume ratio of the partial mixed oxidation liquid to the other partial mixed oxidation liquid is 10-20: in the limitation, most of mixed oxidation liquid is used for preparing mixed acid (including hydrochloric acid and phosphoric acid), and then the mixed acid is reacted with iron powder, so that the reaction rate can be greatly improved, and excessive use of phosphoric acid is avoided, wherein although the related mixed acid contains certain impurities, the requirement of iron dissolution reaction can be met, and 90% of load in a disodium hydrogen phosphate crystallization process is reduced, namely energy consumption is reduced; crystallizing a small part of mixed oxidation liquid to obtain disodium hydrogen phosphate solid, and preparing phosphoric acid, wherein the related phosphoric acid is pure phosphoric acid and is used for an aging reaction of a crude iron phosphate product, so that the purity of the iron phosphate product can be effectively increased.
In the step 5), the ferric phosphate reaction mother liquor is concentrated and then is subjected to membrane separation together with the glyphosate mother liquor, so that the ferric phosphate reaction mother liquor is recycled and reused without newly establishing a wastewater treatment system.
In the step 1), the glyphosate mother liquor refers to: and recovering acid glyphosate mother liquor discharged from a glyphosate production process by using a catalyst triethylamine to obtain alkaline glyphosate mother liquor with the pH value of 9-10, wherein the alkaline glyphosate mother liquor comprises sodium phosphite, glyphosate sodium salt, glyphosine sodium salt, sodium chloride, sodium hydroxide and the like.
In the technical scheme, the 100 percent recovery of phosphorus resources in the glyphosate mother liquor and the self-sufficiency of the phosphorus resources are realized by controlling the mixture ratio of substances in each process.
In addition, the related co-production system of glyphosate and ferric phosphate is as follows:
as shown in fig. 4: the glyphosate production system adopts a glyphosate production system in the existing mature technology, wherein the glyphosate production system comprises a glyphosate separation device;
the iron phosphate production system includes: the glyphosate mother liquor temporary storage tank is connected with the glyphosate separation device, and is connected with the glyphosate separation device;
the organic phosphorus solution oxidation device is arranged on the rear side of a station of the membrane separation device, and an organic phosphorus solution outlet on the membrane separation device is connected with an organic phosphorus solution inlet on the organic phosphorus solution oxidation device; the first bipolar membrane device is arranged at the rear side of a station of the organic phosphorus solution oxidation device, and an upper discharge port of the organic phosphorus solution oxidation device is connected with an upper feed port of the first bipolar membrane device; the iron dissolving device is arranged at the rear side of the station of the first bipolar membrane device, and an acid outlet on the first bipolar membrane device is connected with an acid inlet on the iron dissolving device; the ferrous oxidation kettle is arranged at the rear side of the station of the iron dissolving device, and a solution outlet on the iron dissolving device is connected with the ferrous oxidation kettle; the aging kettle is arranged at the rear side of the working position of the ferrous oxidation kettle, and the ferrous oxidation kettle is connected with the aging kettle; the filtering device is arranged at the rear side of the station of the aging kettle, and the aging kettle is connected with the filtering device; the washing device is arranged at the rear side of the station of the filtering device, and the filtering device is connected with the washing device; the drying box is arranged on the rear side of the station of the washing device, the washing device is connected with the drying box, and the drying box is connected with a finished iron phosphate tank; a continuous passage for preparing iron phosphate by taking the glyphosate mother liquor as a raw material is formed among the glyphosate mother liquor temporary storage tank, the membrane separation device, the organic phosphorus solution oxidation device, the first bipolar membrane device, the iron dissolving device, the ferrous oxidation kettle, the aging kettle, the filtering device, the washing device and the drying box;
a crystallizing device is also arranged at the rear side of the station of the organic phosphorus solution oxidizing device, and an upper discharge port of the organic phosphorus solution oxidizing device is connected with an upper feed port of the crystallizing device; a filtering device is arranged at the rear side of the station of the crystallizing device, and the crystallizing device is connected with the filtering device; a dissolving device is arranged on the rear side of the station of the filtering device, and the filtering device is connected with the dissolving device; a second bipolar membrane device is arranged on the rear side of the station of the dissolving device, the dissolving device is connected with an upper feeding port of the second bipolar membrane device, an upper acid outlet of the second bipolar membrane device is connected with a phosphoric acid temporary storage tank, the phosphoric acid temporary storage tank is connected with a phosphoric acid diluting tank, and the phosphoric acid diluting tank is connected with the aging kettle;
a continuous passage for preparing phosphoric acid by taking the glyphosate mother liquor as a raw material is formed among the glyphosate mother liquor temporary storage tank, the membrane separation device, the organic phosphorus solution oxidation device, the crystallization device, the leaching device, the dissolution device, the second bipolar membrane device, the phosphoric acid temporary storage tank, the phosphoric acid dilution tank and the aging kettle.
Wherein, the ferrous iron oxidation kettle is connected with the membrane separation device, so that the recovery and the reutilization of the ferric phosphate reaction mother liquor can be realized, and a waste water treatment system does not need to be newly built;
the aging kettle is also connected with an iron dissolving device, namely, the aging mother liquor containing phosphoric acid generated in the aging reaction is recycled and reacts with the iron dissolving device, so that the resource saving is realized, and the pollution discharge is reduced.
In addition, a triethylamine recovery tank is arranged between the glyphosate mother liquor temporary storage tank and the membrane separation device, and the triethylamine recovery tank is connected with a liquid caustic soda inlet pipe;
a membrane separation device: comprises a selective permeable membrane and a semi-permeable membrane;
organic phosphorus solution oxidation unit: an oxidant inlet pipe is connected, wherein the organic phosphorus solution is converted into an inorganic phosphorus solution under the action of an oxidant;
a bipolar membrane device: comprises an exchange membrane formed by compounding anions and cations;
and (3) iron melting device: is connected with an iron powder feeding pipe, wherein, the iron powder reacts with mixed acid formed by bipolar membrane treatment to generate ferrous solution;
a ferrous iron oxidation kettle: a hydrogen peroxide inlet pipe is connected, and in a ferrous oxidation kettle, ferrous ions in a ferrous solution and hydrogen peroxide are subjected to oxidation-reduction reaction to generate iron ions, so that preparation conditions are provided for the subsequent generation of iron phosphate;
in an organic phosphorus solution oxidation device, the related principle comprises the following components: oxidizing organic phosphorus into inorganic phosphorus under the action of an oxidizing agent, and enabling the inorganic phosphorus to exist in a solution in a phosphate radical form, wherein the method also comprises the step of oxidizing phosphite radicals into phosphate radicals;
in the first bipolar membrane device, the reaction equation involved includes:
in the iron dissolving device, the involved reaction formula comprises:
in a ferrous oxidation kettle, the involved reaction formula comprises:
in an iron phosphate aging kettle, the involved reaction formula comprises:
in the second bipolar film device, the principle/reaction involved includes:
example 5
Based on example 4, this example discusses the molar ratio of hydrochloric acid to phosphoric acid in the mixed acid, the molar ratio of phosphoric acid to iron powder in the mixed acid, and the iron-dissolving reaction temperature, and the results are shown in table 1.
Example 6
Based on example 2, in this example, the membrane-separated organic phosphorus solution is used as a raw material, and after high-temperature oxidation, cooling and crystallization are performed to obtain disodium hydrogen phosphate dodecahydrate solid, and the catalytic effect of different catalysts on high-temperature oxidation is examined, and the obtained results are shown in table 2 below.
Claims (6)
1. A co-production process for glyphosate and ferric phosphate is characterized by comprising the following steps:
1) membrane separation: carrying out membrane separation on the glyphosate mother liquor under an alkaline condition to obtain an organic phosphorus solution; wherein the mol ratio of chloride ions to phosphorus atoms in the organic phosphorus solution is controlled to be 0-1: 1;
2) high-temperature oxidation: adding an oxidant into the obtained organic phosphorus solution under the conditions of 3-8 Mpa, 200-374 ℃ and a catalyst, and carrying out an oxidation reaction to obtain a mixed oxidation solution containing disodium hydrogen phosphate;
3) electrodialysis: performing electrodialysis on the mixed oxidation liquid obtained in the step 2) to obtain liquid alkali and mixed acid;
the mixed acid comprises phosphoric acid and hydrochloric acid, and the molar ratio of the hydrochloric acid to the phosphoric acid in the mixed acid is controlled to be 0-1: 1;
4) iron dissolving reaction: reacting the obtained mixed acid with iron powder at 30-80 ℃ to obtain ferrous reaction liquid;
wherein the dosage ratio of the phosphoric acid to the iron powder in the mixed acid is 1.5-3: 1;
5) oxidation-reduction reaction: adding hydrogen peroxide into the obtained ferrous reaction liquid, and carrying out redox reaction at the temperature of 30-80 ℃ to obtain iron phosphate slurry; filtering to obtain a crude iron phosphate product and an iron phosphate reaction mother solution;
wherein the molar ratio of the iron powder to the hydrogen peroxide is 1: 0.5-1;
controlling the molar ratio of phosphorus atoms to iron atoms in the crude iron phosphate product to be 1-2: 1;
6) and (3) post-treatment: adding the obtained iron phosphate crude product into an aging kettle by taking the adding amount of a phosphoric acid solution with the concentration of 0.5-5% as 10-20 times of the mass of the iron phosphate crude product, adding a phosphoric acid solution with the concentration of 0.5-5%, aging at the temperature of 80-100 ℃, filtering, washing and drying to obtain an iron phosphate product and an aging mother liquor containing phosphoric acid;
the process for the co-production of glyphosate and ferric phosphate according to claim 1, wherein in step 1), the glyphosate mother liquor is: and recovering an acidic glyphosate mother liquor discharged from a glyphosate production process by using a catalyst triethylamine to obtain an alkaline glyphosate mother liquor with a pH value of 9-10.
2. The process for the co-production of glyphosate and ferric phosphate according to claim 1, characterized in that in step 1), said alkaline conditions are: the pH value is 7-10.
3. The process for co-producing glyphosate and iron phosphate according to claim 1, wherein in step 2), the catalyst is an inorganic salt of one or more transition elements in the fourth period of the periodic table, and the oxidant is oxygen or hydrogen peroxide.
4. The co-production process for glyphosate and ferric phosphate as claimed in claim 1, characterized in that in step 3), part of the mixed oxidation solution obtained is subjected to electrodialysis, the other part of the mixed oxidation solution is subjected to preparation of a phosphoric acid solution with the concentration of 0.5-5%, and the volume ratio of the part of the mixed oxidation solution to the other part of the mixed oxidation solution is controlled to be 10-20: 1;
wherein the preparation process of the phosphoric acid solution with the concentration of 0.5-5% comprises the following steps:
cooling and crystallizing the other part of the mixed oxidation liquid at the temperature of-15-20 ℃, and filtering to obtain a disodium hydrogen phosphate solid;
adding water to dissolve the obtained disodium hydrogen phosphate solid, and controlling to obtain a disodium hydrogen phosphate solution with the concentration of 5-10%;
controlling to obtain a phosphoric acid solution with the concentration of 9-10% under the action of an electric field of a bipolar membrane electrodialysis device;
and diluting the obtained phosphoric acid solution with the concentration of 9-10% to obtain a phosphoric acid solution with the concentration of 0.5-5%.
5. The process for co-producing glyphosate and ferric phosphate according to claim 1, wherein in step 5), the ferric phosphate reaction mother liquor is concentrated and then recycled to the membrane separation step.
6. The process for the co-production of glyphosate and ferric phosphate according to claim 1, characterized in that in step 6), the aged mother liquor containing phosphoric acid is reused in the iron-dissolving reaction step.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115321736A (en) * | 2022-08-24 | 2022-11-11 | 中国科学院过程工程研究所 | Treatment method of glyphosate production wastewater and high-value recycling of phosphorus-containing waste |
| CN115959643A (en) * | 2022-12-05 | 2023-04-14 | 上海安赐环保科技股份有限公司 | Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling |
| CN115959643B (en) * | 2022-12-05 | 2024-05-03 | 上海安赐环保科技股份有限公司 | Method for recycling byproduct phosphate and iron and steel pickling byproduct ferric salt |
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| CN101423281A (en) * | 2008-09-11 | 2009-05-06 | 莫一平 | Glyphosate alkaline mother liquor processing method |
| CN102786187A (en) * | 2012-08-17 | 2012-11-21 | 四川省乐山市福华通达农药科技有限公司 | Integrated process for recycling glyphosate mother liquor |
| CN104944398A (en) * | 2015-06-29 | 2015-09-30 | 江西金龙化工有限公司 | Method for recycling glyphosate mother solution |
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| US5898082A (en) * | 1995-07-25 | 1999-04-27 | Zeneca Limited | Process for the preparation of N-phosphonomethylglycine |
| CN101423281A (en) * | 2008-09-11 | 2009-05-06 | 莫一平 | Glyphosate alkaline mother liquor processing method |
| CN102786187A (en) * | 2012-08-17 | 2012-11-21 | 四川省乐山市福华通达农药科技有限公司 | Integrated process for recycling glyphosate mother liquor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115321736A (en) * | 2022-08-24 | 2022-11-11 | 中国科学院过程工程研究所 | Treatment method of glyphosate production wastewater and high-value recycling of phosphorus-containing waste |
| CN115959643A (en) * | 2022-12-05 | 2023-04-14 | 上海安赐环保科技股份有限公司 | Resource utilization method of byproduct phosphorus salt and byproduct iron salt in steel pickling |
| CN115959643B (en) * | 2022-12-05 | 2024-05-03 | 上海安赐环保科技股份有限公司 | Method for recycling byproduct phosphate and iron and steel pickling byproduct ferric salt |
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